CN104931481B - Laser dual-axis differential confocal induced breakdown Raman spectrum imaging detection method and device - Google Patents

Laser dual-axis differential confocal induced breakdown Raman spectrum imaging detection method and device Download PDF

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CN104931481B
CN104931481B CN201510350428.3A CN201510350428A CN104931481B CN 104931481 B CN104931481 B CN 104931481B CN 201510350428 A CN201510350428 A CN 201510350428A CN 104931481 B CN104931481 B CN 104931481B
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laser
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CN104931481A (en
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赵维谦
王允
邱丽荣
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Beijing Institute of Technology BIT
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Abstract

The invention belongs to spectral measurement and technical field of imaging, it is related to a kind of laser dual-axis differential confocal induced breakdown spectroscopy Raman spectrum imaging detection method and device, high-space resolution imaging and detection available for the microcell component and morphological parameters of sample.This method detects the element composition information of sample component with device using LIBS;Utilize the chemical bond and molecular structure information of Raman spectroscopic detection sample;Sample surface morphology information is detected using dual-axis differential confocal technology, dual-axis differential structure has big visual field, the advantage of big working distance, sample accurately can be focused, it is ensured that illumination spot is minimum, lift excitation of spectra efficiency;Three's combination can be achieved structure and share and have complementary functions, and realize the pattern of sample and the composite measurement of component information.The advantages of present invention has high-space resolution, material composition abundant information and controllable measurement focused spot size, has wide practical use in fields such as mineral products, metallurgy, space exploration, environmental monitoring, biologic medicals.

Description

Laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection method and device
Technical field
The invention belongs to spectral measurement and technical field of imaging, it is related to a kind of laser dual-axis differential confocal induced breakdown-drawing Graceful light spectrum image-forming detection method and device, differential confocal imaging technology is combined with spectrographic detection technology, constitutes a kind of " collection of illustrative plates High-resolution spectra imaging and detection method and the device of unification ", the microcell form component multi-spectrum synthesis available for sample are tested With high-resolution imaging.
Technical background
LIBS (Laser Induced Breakdown Spectroscopy, abbreviation LIBS), It is a kind of material composition in-situ investigation technology, it utilizes the laser excitation sample surfaces of high power density, produces induced with laser etc. Gas ions, by the atom and ion line in exploring laser light induced plasma, to determine that the component of sample is constituted, it is protruded Advantage is that detectable atom is constituted with small molecule element.
Since being born from 1962, LIBS is widely used in minute manufacturing, mineral products analysis, environment The multiple fields such as monitoring, biologic medical, and " chemistry and shooting of " curious number " Marsokhod carrying in U.S.'s transmitting in 2011 Machine instrument system (ChemCam) " be used to carry out remote probe to Mars surface rock sample, show it in space material group Divide the great ability in terms of detection, therefore Venus probe is chosen as again after " curious number " Marsokhod ChemCam systems With instrument, by the widely studied use of the multiple National Airspace structures in the world.
But there is problem following prominent in existing LIBS:
1) sample is excited to produce plasma due to being irradiated using collimated laser beam, thus it still suffers from laser excitation light The problems such as spot is big, spectrographic detection spatial resolution is not high;
2) parameters such as the chemical bond in molecule, molecular structure can not be detected, its result constrains sample material group Divide the accurate complete acquisition of information;
3) it can not effectively suppress back-scattering light interference, constrain the lifting of system signal noise ratio, and and then limit spectrum Detect the improvement of resolving power;
3) the sample component information obtained can not be combined with the shape information of sample, it is impossible to realize sample morphology-group The high-resolution in situ of integrated information is divided to obtain.
And the accurate acquisition of the complete component information of " microcell " of mineral products, space material and biological sample is for scientific research All it is extremely important with production detection.In fact, how to detect micro-area composition information with sensitivity is current mineral products The common technology problem that the fields such as analysis, space exploration and environment measuring are urgently studied.
The intense pulse laser of LIBS, which focuses on sample surfaces, can make sample ionization, can excite sample Plasma is produced, the spectrum given off by detecting energy of plasma decline can obtain the atom and small molecule element of sample Constitute information, but the chemical bond and molecular structure information of sample molecule can not be obtained, how complete acquisition sample molecule Element is constituted and molecular structure information, and the component for high accuracy analysis sample is significant.
Using the molecule excitation spectrum of the measurable sample of laser Raman spectroscopy technology, the chemical bond and molecule in sample are obtained Structural information.Laser Raman spectroscopy technology is combined with LIBS (LIBS) technology, laser can be made up The deficiency of molecular structure and chemical key information can not be obtained in induced breakdown spectroscopy.
Laser dual-axis differential confocal technology is detected using illumination with detection light path non-co- line structure, is not only significantly improved The azimuthal resolution and Focus accuracy of light path, realize the high-resolution imaging detection of sample topography, and can effectively suppress the back of the body To scattering interference, spectrographic detection signal to noise ratio is improved.
Based on this, the present invention proposes a kind of laser dual-axis differential confocal induced breakdown spectroscopy-Raman spectrum micro-imaging side Method and device, its innovation are:First by laser dual-axis differential confocal light path and LIBS (LIBS) technology and Laser Raman spectroscopy Detection Techniques are blended, can be achieved the imaging of sample microcell high-resolution and highly sensitive pattern and component with Detection.
A kind of high-space resolution confocal laser induced breakdown spectroscopy-Raman spectrum micro imaging method proposed by the present invention with Device can provide a brand-new effective technical way for the detection of material composition high-resolution imaging.
The content of the invention
The invention aims to the high-resolution spectra imaging for " collection of illustrative plates " for realizing material composition and shape information, A kind of confocal induced breakdown of laser twin shaft-Raman spectrum imaging detection method and device are proposed, to obtain sample simultaneously Microcell form component multi-spectrum synthesis test and high-resolution imaging.
The purpose of the present invention is achieved through the following technical solutions.
The present invention dual-axis differential confocal laser-induced breakdown-Raman spectrum imaging detection method, light path lighting optical axis with Detection optical axis is distributed into angle, excites light irradiation to be irradiated to sample surfaces along illumination path and inspire and Reyleith scanttering light and is loaded with sample sets The LIBS and Raman spectrum of point information, Reyleith scanttering light, LIBS and Raman spectrum by with illumination Light path is received into the detection light path of angle, and being partly into LIBS detection system by light splitting obtains sample The Raman diffused light that element is constituted in information, another part is obtained through dichroic optical system into Raman spectroscopic detection system The chemical bond and molecular structure information of sample, Reyleith scanttering light and LIBS are reflected into by dichroic optical system Differential confocal detection system carries out light intensity detection and obtains sample surfaces height and topographical information.LIBS detection, Raman spectroscopic detection and the detection triplicity of laser dual-axis differential confocal topographical information can realize that structure shares and had complementary functions, Realize light spectrum image-forming and the detection of high-space resolution, this method to implement step as follows:
1) illumination objective lens are symmetrically distributed in measuring surface normal both sides, and lighting optical axis and measuring surface normal with collection object lens Angle be θ1, the angle of collection optical axis and measuring surface normal is θ2, using measuring surface normal direction as measurement axis, set up system Coordinate system (x, y, z), wherein θ12
2) exciting light is focused on sample via illumination objective lens, is inspired Reyleith scanttering light and is loaded with sample Spectral Properties The Raman spectrum and LIBS of property, the Reyleith scanttering light being inspired and the drawing for being loaded with sample material composition information Graceful spectrum and LIBS are reflected into collection object lens, and collected object lens converge to beam splitting system, light beam warp It is divided into two beams of projection and reflection after beam splitting system light splitting, projecting light path enters LIBS detection system and obtains laser Induced breakdown spectroscopy signal I (λL);The Raman spectrum that the reflected beams are passed through in dichroic optical system light splitting, reflected light passes through two Enter Raman spectroscopic detection system to color beam splitting system and obtain raman spectral signal I (λR), Reyleith scanttering light in the reflected beams and swash Photoinduction breakdown spectral is reflected into differential detection system by dichroic optical system;
3) differential processing is carried out to the optical signal for entering differential detection system, wherein, in differential detection system two it is identical Detection system it is symmetrically placed in measurement optical axis both sides, differential confocal is obtained to the signal subtraction processing of two detection systems bent Line, and obtain differential wave I (x, y, z, vxM), wherein vxMIt is detection system transversal displacement, utilizes differential confocal curve zero passage Point and the accurate corresponding characteristic in focal position, excitation beam focus O positions are accurately positioned by zero point triggering, detected sample is realized The focus positioning of the high-space resolution of product;
4) according to differential wave I (x, y, z, vxM) control laser beam accurately to focus on sample, reacquire quilt Spectral signal I (the λ of test sample productL) and I (λR);
5) data handling system is utilized by differential wave I (x, y, z, the v of acquisitionxM), spectral signal I (λL) and I (λR) enter Row Data Fusion, to obtain the topographical information of sample and four-dimensional metrical information I (x, y, z, the λ of material composition informationLR);
6) complete after above-mentioned steps, control light beam is scanned detection to sample, next to sample surface Point repeat step 2), 3), 4), 5) until scanning complete;
7) differential wave I (x, y, z, v are individually handledxM) when, obtain the three-dimensional appearance letter of the high-space resolution of sample Breath;Individually handle raman spectral signal I (λR) when, obtain the chemical bond and molecular structure information of sample;Individually processing swashs Photoinduction breakdown spectral signal I (λL) when, obtain the element composition information of sample;While processing differential wave I (x, y, z, vxM), spectral signal I (λL) and I (λR) when, obtain high-space resolution pattern and " the collection of illustrative plates conjunction of microcell material composition of sample One " imaging detection;
Two identical detection systems in the present invention in differential detection system can also be single detection system i.e. One detector, data handling system is obtained after focal spot pattern from the first detector, calculates the center of now focal spot pattern, Using this center as the origin of coordinates, the coordinate system (x set up in detector image planesd′,yd'), in xdTwo tools are symmetrical arranged on ' axle The circular pin hole focal spot pattern for having same radius carries out segmentation detection, respectively the first dummy pinhole and the second dummy pinhole, Its position corresponds to above-mentioned two detection system respectively, when sample is scanned, and data handling system calculates the respectively Pixel grey scale summation in the range of one dummy pinhole and the second dummy pinhole, obtains intensity response.
Focused spot size being measured for compression in the present invention and improving system transverse resolution, the excitation beam is polarization Light beam, including line polarisation, rotatory polarization, radial polarisation light;Or the structure light beam generated by pupil filtering technology.
System in the present invention can also detect the scattering spectrums such as fluorescence, Compton scattering light.
The present invention provides a kind of dual-axis differential confocal laser-induced breakdown-Raman spectrum imaging detection device, including light source, Illumination objective lens and collection object lens, it is characterised in that:Also include light-beam scanner, collimator and extender mirror, beam splitting system, dichroic point Photosystem, differential detection device, Raman spectroscopic detection system and LIBS detection system;Wherein, illumination objective lens Symmetrically it is laid out in measuring surface normal both sides with collection object lens, the angle of lighting optical axis and measuring surface normal is θ1, gather optical axis Angle with measuring surface normal is θ2, wherein θ12, collimator and extender mirror, light-beam scanner and illumination objective lens are successively placed on light The emergent ray direction in source, collection object lens and beam splitting system are successively placed on the reflection light direction of sample, and induced with laser is hit Wear spectrum investigating system and be placed on dichroic light-dividing device transmission direction, dichroic optical system and Raman spectroscopic detection system are placed In the reflection direction of beam splitting system, differential detection device is placed on the reflection direction to color beam splitting system.
It is raising system transverse resolution in apparatus of the present invention, system can also add between collimator and extender mirror and illumination objective lens Enter illumination end iris filter, or addition collection terminal iris filter, Huo Zhe between spectroscope and differential detection device Illumination end iris filter is added between collimator and extender mirror and illumination objective lens and between spectroscope and differential detection device simultaneously With collection terminal iris filter.
It is raising system transverse resolution in apparatus of the present invention, can also adds between collimator and extender mirror and light-beam scanner Enter polarization modulating arrangement, or polarization modulating arrangement is added between illumination objective lens and illumination end iris filter.
The detection device of differential detection device can be ccd detector in apparatus of the present invention, or two parameters are identical Point probe.
Also include the last data handling system for carrying out Data Fusion in apparatus of the present invention.
Raman spectroscopic detection device can be confocal spectroscopic detection device in apparatus of the present invention, including the first condenser, position In the pin hole of the first condenser focal point, second condenser lens, after the spectrometer and spectrometer of second condenser lens focal point Second detector;It can also be common spectral detection device, including second condenser lens, the light positioned at second condenser lens focal point The second detector after spectrometer and spectrometer;LIBS detection device includes laser-induced breakdown condenser, position Spectrometer and the 3rd detector after pin hole in laser-induced breakdown condenser focal position, pin hole.
Beneficial effect
The inventive method, contrast prior art has following innovative point:
1) present invention organically combines laser dual-axis differential confocal technology and spectrographic detection technology, has merged laser twin shaft poor The high-precision axial tracking of dynamic confocal technology focuses ability, and accurate focus can be carried out to sample and ensures that focused activating light spot is minimum, And then the spectrum parameter that sample minimum excites focal beam spot region is obtained, the high-space resolution detection of sample microscopic spectrum is realized, This is to be different from one of innovative point of existing spectrographic detection technology;
2) present invention is by being rationally designed to raman scattering spectrum and laser-induced breakdown light to containing different information Spectrum is detected simultaneously, realizes that structure shares and had complementary functions, and is realized to sample element composition and chemical bond and molecular structure High-resolution detection, obtain sample material component integrated information, this be different from existing spectrographic detection technology innovative point it Two;
3) using the characteristic of the different focused spot sizes of the confocal response curve range of linearity correspondence of laser twin shaft, to focusing on light Spot position carries out accuracy controlling, and then controls the size of measurement focal beam spot, is easy to survey the sample of different testing requirements Examination and analysis, that is, realize that measurement focused spot size is adjustable, this is the three of the innovative point for being different from existing spectrographic detection technology;
4) laser cross-compound arrangement is it is possible to prevente effectively from the system veiling glare that excitation beam backscattering is introduced, reduction spectrum is visited Noise is surveyed, detection signal to noise ratio and Spectral resolution is improved, this is the four of the innovative point for being different from existing spectrographic detection technology;
The inventive method has following features:
1) fusion laser dual-axis differential confocal technology and spectrographic detection technology, utilize the accurate of differential confocal system focusing Positioning, greatly improves the spatial resolution of spectrographic detection;
2) can be combined by LIBS and laser Raman spectroscopy, realize excite with detecting structure share and The complementation of function, obtains the integrated informations such as element composition, chemical bond and the molecular structure of sample component;
3) illuminate and detect by the way of cross-compound arrangement oblique incidence, effectively inhibit the interference of focal plane sample scattered light, Improve spectrographic detection signal to noise ratio;
4) using the laterally differential photon excited of division focal spot, it is easy to system to change the object lens of different NA values according to demand, It is easy to adjust, and can realize that range ability and the effective of resolution capability take into account.
Brief description of the drawings
Fig. 1 is laser differential confocal imaging detection light path
Fig. 2 is two-axis laser differential confocal laser-induced breakdown-Raman spectrum imaging detection method schematic diagram;
Fig. 3 is simple detector two-axis laser differential confocal laser-induced breakdown-Raman spectrum imaging detection method schematic diagram;
Fig. 4 is dual-axis differential signal detection process schematic;
Fig. 5 is laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection device schematic diagram;
Fig. 6 is that laser dual-axis differential confocal laser-induced breakdown-Raman spectrum imaging detection device with Polarization Modulation is shown It is intended to;
Fig. 7 is that laser dual-axis differential confocal laser-induced breakdown-Raman spectrum imaging detection method shows with device embodiment 1 It is intended to;
Fig. 8 is that laser dual-axis differential confocal laser-induced breakdown-Raman spectrum imaging detection method shows with device embodiment 2 It is intended to;
Wherein, 1- light sources, 2- illumination objective lens, 3- samples, 4- lighting optical axis, 5- measuring surface normals, 6-θ1, 7- collections Object lens, 8- beam splitting systems, 9- measurement lens, 10- microcobjectives, the detection systems of 11- first, the detection systems of 12- second, 13- is surveyed Measure optical axis, 14- pin hole transversal displacements, 15- differential detection systems, 16- focal spot patterns, 17- the second detection system hot spots, 18- First detection system hot spot, 19- Raman spectroscopic detection systems, 20- Ramans collection optical axis, 21- data handling systems, 22- first Detector, the dummy pinholes of 23- second, the dummy pinholes of 24- first, 25- collimating and beam expanding systems, 26- light-beam scanners, 27- is poor Dynamic confocal curves, 28- illumination end iris filters, 29- polarization modulating arrangements, 30- collection terminal iris filters, 31- first gathers Light microscopic, 32- pin holes, 33- second condenser lens, 34- Raman spectrometers, 35- Raman spectroscopy detectors, the confocal Raman curves of 36-, 37-θ2, 38- dichroic optical systems, 39- LIBS detection systems, 40- LIBSs collection light Axle, 41- LIBS condensers, 42- pin holes, 43- laser induced breakdown spectrographs, 44- laser-induced breakdown light Compose detector, 45- confocal laser induced breakdown spectroscopy light intensity curves.
Embodiment
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1
In the present embodiment, light source 1 is laser, and polarization modulating arrangement 29 is radial polarisation photogenerator, dichroic light splitting System 38 is Notch filter, and data handling system 21 is computer, and the first detector 22 is the first ccd detector, Raman Spectral detector 35 is spectrum ccd detector.
As shown in Fig. 3, Fig. 4 and Fig. 7, illumination objective lens 2 are symmetrically distributed in the both sides of measuring surface normal 5 with collection object lens 7, and The angle of lighting optical axis 4 and measuring surface normal 5 is θ16, the angle of collection optical axis 20 and measuring surface normal 5 is θ237, wherein θ12, using the direction of measuring surface normal 5 as measurement axis, set up system coordinate system (x, y, z), high-space resolution dual-axis differential confocal Collection of illustrative plates micro imaging method, its measuring process is:
First, after the collimated beam-expanding system 25 of light beam that laser 1 is sent, progress is expanded to be turned into and illumination objective lens after outgoing The equal directional light of 2 Entry pupil diameters, turns into radial polarisation light, radial polarisation light is through illumination after radial polarisation photogenerator 29 Light beam is modulated after the iris filter 28 of end, and forming compression hot spot by illumination objective lens 2 after light-beam scanner 26 focuses on The surface of sample 3, inspires Reyleith scanttering light and is dissipated with the Raman diffused light and laser-induced breakdown for being loaded with the spectral characteristic of sample 3 Light is penetrated, sample 3 can strengthen technology by spectrum such as enhanced spectrum nano-particles and be handled, to improve the strong of scattered light Degree.
Axial (Z-direction i.e. in figure) sample 3, makes Reyleith scanttering light and corresponds to the different zones of sample 3 when mobile Raman diffused light is reflected into collection object lens 7, and the light beam collected by gathering object lens 7 is split the light splitting of system 8:
Enter laser-induced breakdown through the Reyleith scanttering light of beam splitting system 8, Raman diffused light and laser-induced breakdown scattered light Spectrum investigating system 39, assembles by LIBS condenser 41 and enters LIBS by pin hole 42 Instrument 43 is simultaneously detected the LIBS I (λ for obtaining sample 3 by LIBS detector 44L)(λLFor LIBS).
Reyleith scanttering light, Raman diffused light and the laser-induced breakdown scattered light that the system that is split 8 reflects are by Notch filter 38 light splitting again:
Raman diffused light transmitted through Notch filter 38 enters spectrum investigating system 19, and spectrum investigating system 19 is Confocal Raman spectra detection system, Raman diffused light converges to pin hole 32 by the first condenser 31, by the meeting of second condenser lens 33 It is poly- to enter Raman spectrometer 34, Raman spectroscopy detector 35 is finally incided, the Raman spectrum I (λ of sample 3 are obtainedR)(λR For Raman spectrum).
Collection terminal iris filter 30 is passed through by the Reyleith scanttering lights reflected of Notch filter 38 and LIBS After modulation, carry out converging to differential detection system 15 by measuring lens 9, convergence hot spot amplifies and is imaged by microcobjective 10 On the first ccd detector 22.
In measurement process, computer 21 obtains focal spot image 16 from the first ccd detector 22, calculates now focal spot figure As 16 center, using this center as the origin of coordinates, the coordinate system (x set up in CCD image planesd′,yd'), in xdSymmetrically set on ' axle Put two circular dummy pinhole focal spot images 16 with same radius and carry out segmentation detection, respectively the first dummy pinhole 24 and second dummy pinhole 23, its corresponding pin hole transversal displacement 14 is M;When sample 3 is scanned, computer 21 Pixel grey scale summation in the range of the first dummy pinhole 24 and the second dummy pinhole 23 is calculated respectively, and focal spot image is corresponded to respectively The first detection system hot spot 18 and the second detection system hot spot 17 in 16, obtain intensity response I1(x,y,z,-vxM) and I2(x, y,z,+vxM), wherein vxMIt is pin hole transversal displacement, x, y, z is coordinate of the sample under system coordinate system.
Computer 21 is to I1(x,y,z,-vxM) and I2(x,y,z,+vxM) carry out it is differential subtract each other processing, obtain with detected sample Intensity response I (x, y, z, the v of the convex-concave of product 3 changexM),
I(x,y,z,vxM)=I1(x,y,z,-vxM)-I2(x,y,z,+vxM) (1)
Corresponding differential confocal curves 27 are fitted according to the result of formula (1), using the zero crossing of differential confocal curve 27 with The accurate corresponding characteristic in focal position, obtains system focus O position, and sample 3 is moved into focus O positions.So this When can Raman spectrum I (λ of the recapture sample 3 at focus OR) and LIBS I (λb)。
By I (λR)、I(λL)、I(x,y,z,vxM) the progress data processing of computer 21 is sent to, so as to obtain comprising tested Sample 3 positional information I (x, y, z, vxM) and spectral information I (λR) and I (λL) four-dimensional metrical information I (x, y, z, λRL)。
Complete after above-mentioned steps, transversal scanning is carried out to sample 3, and obtain positional information and spectral information again.
Pass through said process, you can obtain accurate spectral information, realize the spectrographic detection and three-dimensional geometry of focal position Position sensing, wherein, by metrical information { I (x, y, z), I (λR), I (λL) fusion treatment, can be achieved formula (2) shown in Three kinds of measurement patterns, i.e.,:The test of microcell collection of illustrative plates tomography, three dimension scale tomography and spectrum test.
When θ=45 °, lighting optical axis 4 and collection optical axis 20 are mutually perpendicular to, and now the Reyleith scanttering light light intensity of sample 3 is most It is weak, be conducive to the high scattering biological sample of systematic observation.
As shown in fig. 6, high-space resolution dual-axis differential confocal induced breakdown-Raman spectrum imaging detection device is included along light Laser 1 that road is sequentially placed, collimating and beam expanding system 25, radial polarisation photogenerator 29, illumination end iris filter 28, light beam Scanning means 26, illumination objective lens 2, sample 3, and the collection object lens 7 of light path reflection direction, beam splitting system 8, positioned at light splitting system The LIBS system 39 for 8 transmission directions of uniting, positioned at the Notch filter 38 of the reflection direction of beam splitting system 8, Positioned at the differential detection system 15 of the reflection directions of Notch filter 38, positioned at the Raman of the transmission directions of Notch filter 38 Spectrum investigating system 19, and connection differential detection system 15, LIBS system 39 and Raman spectroscopic detection system 19 computer 21;Wherein, Raman spectroscopic detection system 19 include be sequentially placed along light path the first condenser 31, positioned at first The pin hole 32 of the focal position of condenser 31, the second condenser lens 33 after pin hole 32, positioned at the focal position of second condenser lens 33 Raman spectrometer 34 and the spectrum ccd detector 35 after spectrometer;LIBS detection system 39, including The poly- mirror 41 of LIBS that is sequentially placed along light path, positioned at the focal position of LIBS convergent mirror 41 Pin hole 42, laser induced breakdown spectrograph 43 and LIBS detector 44 after pin hole 42;Differential detection System 15 includes being located at the microcobjective 10 of the measurement focal point of lens 9, and positioned at the first CCD detection of the focal point of microcobjective 10 Device 22.
Embodiment 2
In the present embodiment, Polarization Modulation system 29 is radial polarisation photogenerator, and dichroic optical system 38 is Notch Filter, the point probe of the first detection system 11 first, the point probe of the second detection system 12 second, data handling system 21 is Computer, the first detector 22 is the first ccd detector, and Raman spectroscopy detector 35 is spectrum ccd detector.
As shown in Fig. 2, Fig. 5, Fig. 6 and Fig. 8, the first ccd detector in the Fig. 7 of embodiment 1 is replaced with to Fig. 8 two ginsengs Number identical point probe, is the first point probe 11 and the second point probe 12 respectively, you can constitute embodiment 2.First point Position where 11 and second point probe of detector 12 respectively with the first dummy pinhole 24 of embodiment 1 and the second dummy pinhole Position correspondence where 23.Position where first dummy pinhole 24 and the second dummy pinhole 23 can in advance be counted according to systematic parameter Draw.
When carrying out axial scan to sample, if when sample 3 is located on system focal plane being system initial position, this When test surface on the center of focal spot 16 and (xd,yd) coordinate origin overlaps, shown in such as Fig. 4 (1), now the first point probe 11 It is identical with the signal magnitude that the second point probe 12 is detected, it is differential subtract each other after signal magnitude be zero, i.e., this is characteristic Dead-center position correspondence system focal position.When sample 3 is moved along z-axis to close lens direction, now on test surface Focal spot position such as Fig. 4 (2) and 4 (3) shown in, focal spot center levels off to the second point probe 12, and the second point probe 12 is received Initial position shown in the light intensity arrived such as Fig. 4 (1) is big;On the other hand, focal spot center now is relative to the first point probe 11 are in away from state, and therefore, the beam intensity ratio initial position that the first point probe 11 is received is small, then now by first point The signal I of detector 111(x,y,z,-vxM) and the second point probe 12 signal I2(x,y,z,+vxM) subtract each other obtain differential Signal I (x, y, z, vxM) relative to the differential wave reduction of initial position.Similarly, when sample 3 is along z-axis to away from object lens When direction is moved, now such as Fig. 4 of the focal spot position on test surface (4) and 4 (5) are shown, and focal spot center levels off to first point of detection Device 11, the beam intensity ratio initial position that the first point probe 11 is received is big, and at the beginning of the beam intensity ratio that the second point probe 12 is received Beginning, position was small, then differential wave I (x, y, z, v nowxM) relative to the differential wave increase of initial position.Drive detected sample Product 3 are moved along z-axis as axial scan, and the signal that the first point probe 11 and the second point probe 12 are detected carries out differential Subtract each other, you can obtain receptance function I (x, y, z, the v of dual-axis differential confocal microtechnicxM).Curve 27 in Fig. 4 is that twin shaft is poor Axial response function I (x, y, z, the v of dynamic confocal microscopyxM) schematic diagram.
Remaining measuring method and device are same as Example 1.
The embodiment of the present invention is described above in association with accompanying drawing, but these explanations can not be understood to limitation The scope of the present invention, protection scope of the present invention is limited by appended claims, any in the claims in the present invention base Change on plinth is all protection scope of the present invention.

Claims (10)

1. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection method, it is characterised in that:Light path lighting optical axis with Detection optical axis is distributed into angle, excites light irradiation to be irradiated to sample surfaces along illumination path and inspire and Reyleith scanttering light and is loaded with sample sets The LIBS and Raman spectrum of point information, Reyleith scanttering light, LIBS and Raman spectrum by with illumination Light path is received into the detection light path of angle, and being partly into LIBS detection system by light splitting obtains sample The Raman diffused light that element is constituted in information, another part is obtained through dichroic optical system into Raman spectroscopic detection system The chemical bond and molecular structure information of sample, Reyleith scanttering light and LIBS are reflected into by dichroic optical system Differential confocal detection system carries out light intensity detection and obtains sample surfaces height and topographical information;LIBS detection, Raman spectroscopic detection and the detection triplicity of laser dual-axis differential confocal topographical information can realize that structure shares and had complementary functions, real The light spectrum image-forming of existing high-space resolution and detection, this method to implement step as follows:
1) illumination objective lens (2) are symmetrically distributed in measuring surface normal (5) both sides with collection object lens (7), and lighting optical axis (4) are with surveying The angle of amount face normal (5) is θ1(6), the angle of collection optical axis (20) and measuring surface normal (5) is θ2(37), with measuring surface method Line (5) direction is measurement axis, sets up system coordinate system (x, y, z), wherein θ12
2) exciting light is focused on sample (3) via illumination objective lens (2), is inspired Reyleith scanttering light and is loaded with sample spectrum The Raman spectrum and LIBS of characteristic, the Reyleith scanttering light being inspired and be loaded with sample (3) material composition letter The Raman spectrum and LIBS of breath are reflected into collection object lens (7), and collected object lens (7) converge to light splitting System (8), light beam is divided into two beams of transmission and reflection after beam splitting system (8) light splitting, and transmitted light path enters laser-induced breakdown light Compose detection system (19) and obtain LIBS signal I (λL);The reflected beams are by dichroic optical system (38) point Raman spectrum in light, reflected light enters Raman spectroscopic detection system (39) through dichroic optical system (38) and obtains Raman light Spectrum signal I (λR), Reyleith scanttering light and LIBS in the reflected beams are reflected into by dichroic optical system (38) Differential detection system (15);
3) differential processing is carried out to the optical signal for entering differential detection system (15), wherein, two in differential detection system (15) Identical detection system (11,12) is symmetrically placed in measurement optical axis (13) both sides, to detection system (11) and the signal phase of (12) Subtract processing and obtain differential confocal curve (27), and obtain differential wave I (x, y, z, vxM), wherein vxMIt is detection system (11,12) Transversal displacement, using the accurate corresponding characteristic in differential confocal curve zero crossing and focal position, by zero point triggering come accurate Localized excitation beam focus O positions, realize the focus positioning of the high-space resolution of sample;
4) according to differential wave I (x, y, z, vxM) control laser beam accurately to focus on sample (3), reacquire tested Spectral signal I (the λ of sample (3)L) and I (λR);
5) data handling system (21) is utilized by differential wave I (x, y, z, the v of acquisitionxM), spectral signal I (λL) and I (λR) carry out Data Fusion, to obtain the topographical information of sample and four-dimensional metrical information I (x, y, z, the λ of material composition informationLR);
6) complete after above-mentioned steps, control light beam is scanned detection to sample (3), next to sample (3) surface Individual repeat step 2), 3), 4), 5) until scanning complete;
7) differential wave I (x, y, z, v are individually handledxM) when, obtain the three-dimensional appearance letter of the high-space resolution of sample (3) Breath;Individually handle raman spectral signal I (λR) when, obtain the chemical bond and molecular structure information of sample (3);Individually processing LIBS signal I (λL) when, obtain the element composition information of sample (3);Differential wave I is handled simultaneously (x,y,z,vxM), spectral signal I (λL) and I (λR) when, obtain the high-space resolution pattern and microcell material group of sample (3) Divide the imaging detection of " collection of illustrative plates ".
2. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection method according to claim 1, its feature It is:Two identical detection systems (11,12) in differential detection system (15) can also be single detection system i.e. One detector (22), data handling system (21) is obtained after focal spot pattern (16) from the first detector (22), is calculated now The center of focal spot pattern (16), using this center as the origin of coordinates, the coordinate system (x set up in detector image planesd′,yd'), xdTwo circular pin holes with same radius are symmetrical arranged on ' axle segmentation detection is carried out to (23,24) focal spot pattern (16), point Not Wei the first dummy pinhole (24) and the second dummy pinhole (23), its position respectively correspond to above-mentioned two detection system (11,12), When sample (3) is scanned, data handling system (21) calculates the first dummy pinhole (24) and second virtual respectively Pixel grey scale summation in the range of pin hole (23), obtains intensity response.
3. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection method according to claim 1, its feature It is:For compression measurement focused spot size and improve system transverse resolution, the excitation beam is light beam, including line Polarisation, rotatory polarization, radial polarisation light;Or the structure light beam generated by pupil filtering technology.
4. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection method according to claim 1, its feature It is:The system can also detect the scattering spectrums such as fluorescence, Compton scattering light.
5. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection device, including light source (1), illumination objective lens (2) and Gather object lens (7), it is characterised in that:Also include light-beam scanner (26), collimator and extender mirror (25), beam splitting system (8), two to Color beam splitting system (38), differential detection device (15), Raman spectroscopic detection system (19) and LIBS detection system Unite (39);Wherein, illumination objective lens (2) and collection object lens (7) are symmetrically laid out in measuring surface normal (5) both sides, lighting optical axis (4) Angle with measuring surface normal (5) is θ1(6), the angle of collection optical axis (20) and measuring surface normal (5) is θ2(37), wherein θ12, collimator and extender mirror (25), light-beam scanner (26) and illumination objective lens (2) are successively placed on the emergent ray side of light source (1) To collection object lens (7) and beam splitting system (8) are successively placed on the reflection light direction of sample (3), LIBS Detection system (39) is placed on dichroic light-dividing device (8) transmission direction, dichroic optical system (38) and Raman spectroscopic detection system System (19) is placed on the reflection direction of beam splitting system (8), and differential detection device (15) is placed on to the anti-of color beam splitting system (38) Penetrate direction.
6. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection device according to claim 5, its feature It is:To improve system transverse resolution, system can also add illumination end between collimator and extender mirror (25) and illumination objective lens (2) Iris filter (28), or the addition collection terminal iris filter between dichroic optical system (38) and measurement lens (9) (30), or between collimator and extender mirror (25) and illumination objective lens (2) and dichroic optical system (38) and differential detection dress Put between (15) while adding illumination end iris filter (28) and collection terminal iris filter (30).
7. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection device according to claim 5 or 6, its It is characterised by:To improve system transverse resolution, it can also be added between collimator and extender mirror (25) and light-beam scanner (26) Polarization modulating arrangement (29), or add polarization modulating arrangement between illumination objective lens (2) and illumination end iris filter (28) (29)。
8. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection device according to claim 5 or 6, its It is characterised by:The detection device of differential detection device (15) can be ccd detector, or two parameter identical points detections Device.
9. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection device according to claim 5, its feature It is:Also include the last data handling system (21) for carrying out Data Fusion.
10. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection device according to claim 5 or 6, its It is characterised by:Raman spectroscopic detection device (19) can be confocal spectroscopic detection device, including the first condenser (31), positioned at Pin hole (32), second condenser lens (33), the spectrometer (34) positioned at second condenser lens (33) focal point of one condenser focal point And the second detector (35) after spectrometer (34);It can also be common spectral detection device, including second condenser lens (33), The second detector (35) after the spectrometer (34) and spectrometer (34) of second condenser lens (33) focal point;Induced with laser is hit Wearing spectral detection device (39) includes laser-induced breakdown condenser (41), positioned at laser-induced breakdown condenser (41) focus position Spectrometer (43) and the 3rd detector (44) after the pin hole (42) put, pin hole (42).
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